Method of making n-aryl thiazylsulfenamides



Patented July 10, 1951 METHOD OF MAKING N-ARYL THIAZYLSULFENAMIDES George E. P. Smith, Jr., and Edward L. Carr, Akron, Ohio, assignors to The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio N Drawing. Application November 21, 1947,

Serial No. 787,480

4 Claims. (01. 260 -3063) This invention relates to N-aryl thiazyl sulfenamides and the method of making the same. To prepare these compounds, an unsubstituted. thiazylsulfenamide is mixed with an aryl amine 4-methylbenzothiazyl 2-sulfenamide 5-ethylbenzothiazyl 2-sulfenamide S-tert-Butylbenzothiazyl 2-sulfenamide Thiazyl 2-sulfenamide having at least one replaceable hydrogen atom 5 4,5-dimethylthiazyl 2-sulfenamide directly connected to the amino nitrogen atom. 4,5-diethylthiazyl 2-su1fenamide In the course of the reaction ammonia is elimi- 4-methylthiazyl 2-su1fenamide nated, and the rate of evolution of ammonia is 4-ethylthiazyl 2-sulfenamide a measure of the progress of the reaction. The 4-butylthiazyl 2-sulfenamide ammonia may be recovered if desired. 5-ethy1thiazy1 z-sulfenamide It is often convenient to use a solvent to facilitate mixing the reactants. Such solvent may be fig fg? Solvents for the process Include the inert. In many cases an excess of amine may be used as the solvent. The reaction may be carol ried out in a water suspension or in a mixed Ethanol solvent, such as alcohol-water mixtures or in a Propanol solvent immiscible with water. Using the prea l ferred reactant ratio an excess of the amine is r am de employed. Dimethylformamide Exemplary of amines for the purpose of reactgo th ing with any thiazyl sulfenamide as described, are iO ane the following: Benzene p-tert-Amylaniline g igf z p-Phenetidine y p-Anisidine 35 Toluene Glycolmonomethyl ether p'Phenylamlme Glycol-diethylether 2,4-dimethylani1ine 2,4-diamy1aniline The following example in which parts are my 2,5-dimethy1aniline weight further illustrates the invention: 3,5-dimethylaniline Thirty-one grams (0.3 mole) aniline and 18.23 2,4,6-trimethy1ani1in grams (0.1 mole) unsubstituted benzothiazyl 2,3,5-trimethylaniline 2-sulfenamide were heated at 70-80 C. for 1 hour 2,3,4,5-tetramethy1a,ni1ine under a vacuum which aided in the removal of Pentamethylaniline ammonia as formed. The reaction mixture, on Beta-naphthylamine standing over night at room temperature, turned Alpha-naphthylamine to a dark brown liquid. This was extracted with Methyl-beta-naphthylamine two 100 cc. portions of petroleum ether to remove Butyl-beta-naphthylamine the excess aniline. The residue was dissolved in Dibutyl-beta-naphthy1amine 200 cc. of ether, leaving insoluble matter which Octyl-beta-naphthylamine 40 was believed to be benzothiazyldisulfide. Onre- Butyl-alpha-naphthylamine moval of the ether, N-phenylbenzothiazyl 2-sul- Aniline fenamide remained. It was identified by the D-Toluidine usual test for sulfenamides; namely, reduction p-Butylaniline with sodium hydrosulfite which gave mercaptoo-Toluidine benzothiazole. The latter was identified by melt- Exemplary of thiazyl sulfenamides which may mm and mlxed meltmg pomt determma' gfi sgg fig g ggg of the ammes as aforesald' Similarly, other amines may be reacted with other thiazyl 2-sulfenamides. This application is i Yl -Su enamide a continuation of our application S. N. 690,336 Naphthothiazyl2-su1fenamide filed August 13, 1946, now abandoned. The ins-chlolobenzothiazyl Z-sulfenamide vention is defined in the appended claims. 4-ethoxybenzothiazyl 2-sulfenamide What we claim is: fi-phenylbenzothiazyl Z-sulfenamide 1. A method of preparing sulfenamides which fi-nitrobenzothiazyl 2-sulfenamide comprises reacting an arylene thiazyl 2-sulfenamide having an unsubstituted amide group with an aryl amine having at least one replaceable hydrogen atom directly connected to the amino nitrogen atom.

2. A methodof preparing sulienamides which comprises reacting an arylene thiazyl 2-sulfenamide having an unsubstituted amide group with aniline.

3. A method of preparing sulfenamides which comprises reacting a thiazyl 2-sulfenamide having an unsubstituted amide group with an aryl amine having at least one replaceable hydrogen atom directly connected to the amino nitrogen atom.

4. The method of preparing N-phenylbenzothiazyl-2-sulfenamide which comprises heating aniline with benzothiazyl-2-su1fenamide, in the ratio of at least one mole of aniline per mole of sulfenamide, under a vacuum to aid in removing gaseous ammonia as formed during the resulting reaction, and separating the desired substituted benzothiazyl-2-su1fenamide from the reaction mixture.

GEORGE E. P. SMITH, JR.

EDWARD L. CARR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,370,253 Messer Feb. 27, 1945 2,382,793 Howland Aug. 14, 1945 2,476,818 Carr et al. July 19, 1949 

1. A METHOD OF PREPARING SULFENAMIEDS WHICH COMPRISES REACTING AN ARYLENE THIAZYL 2-SULFENAMIDE HAVING AN UNSUBSTITUTED AMIDE GROUP WITH AN ARYL AMINE HAVING AT LEAST ONE REPLACEABLE HYDROGEN ATOM DIRECTLY CONNECTED TO THE AMINO NITROGEN ATOM. 